CN103980204B - 离子液体催化胺类与α，β－不饱和缺电子受体方法 - Google Patents

离子液体催化胺类与α，β－不饱和缺电子受体方法 Download PDF

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CN103980204B
CN103980204B CN201410232906.6A CN201410232906A CN103980204B CN 103980204 B CN103980204 B CN 103980204B CN 201410232906 A CN201410232906 A CN 201410232906A CN 103980204 B CN103980204 B CN 103980204B
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应安国
侯海亮
胡华南
武承林
李嵘嵘
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Taizhou kejinzhong high tech transfer Co.,Ltd.
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Abstract

本发明涉及一种绿色、高效催化胺类和α，β－不饱和缺电子受体的Michael加成方法。所述方法包括以离子液体为催化剂，室温、常压下胺类和丙烯酸酯、丙烯腈等α，β－不饱和缺电子受体进行催化加成反应，柱层析得到相应的加成产物。无溶剂室温磁搅拌，反应完成后用水和乙酸乙酯萃取离子液体，有机相经柱层析得到产品，包含离子液体水相的滤液可在高温真空下蒸发水分后再次投入反应，经验证，可作为催化反应体系6次重复使用，未见明显的反应收率下降。该法操作简单、收率高、催化反应体系可重复使用性好、反应条件温和，具有良好的工业化前景。

Description

离子液体催化胺类与α，β－不饱和缺电子受体方法
技术领域
本发明涉及一种高效、绿色、以新型功能离子液体为催化剂的Michael加成胺类和α，β－不饱和缺电子受体方法。
技术背景
Michael加成反应是有机合成中形成碳碳双键的非常有效的方法之一，常用于亲电的共轭体系(电子受体)与亲核的负碳离子(电子给体)进行的共轭加成反应，例如胺类与α，β－不饱和缺电子受体的加成。Michael加成是以碱为催化剂，有机溶剂为反应介质的反应。通常使用的均相碱性催化剂主要包括乙醇钠、氢化钠、氨基钠和有机碱等。以上方法虽然取得了一些成果，但是这些方法或多或少存在着一些问题，如：收率不高、后处理繁琐和一些有毒有害溶剂的使用。因此，开发高效、绿色的Michael加成方法不仅具有重要的经济效益，而且还有良好的环境和社会效益。
近几年来，功能离子液体为人们指出了探索绿色环保的催化反应体系的重要方向。离子液体本身具有特殊的物化特性和热力学稳定性、溶解能力强、低挥发性、分子结构可调性等特点，使其成功应用于催化反应(用作溶剂或催化剂)，后处理简单，可多次重复使用，表现出非常优异的特点。因此，利用新开发的功能离子液体催化Michael加成反应是很有必要的。
发明内容
本发明的目的是取代传统的碱催化Michael加成胺类和α，β－不饱和缺电子受体的方法，提供一种高效、环境友好的催化剂和反应介质，温和反应条件下实现Michael加成。
根据本发明，所述Michael加成胺类和α，β－不饱和缺电子受体的方法，包括以离子液体为催化剂，室温、常压下胺类和α，β－不饱和缺电子受体进行催化加成反应100～500分钟，柱层析得到相应的加成产物；其中，所述离子液体为：
其中，所述胺类与α，β－不饱和缺电子受体的摩尔比为1:1～1:2。
其中，所述离子液体的摩尔量为胺类的0.01～1倍。
其中，所述胺类为吗啉、咪唑、吡唑、4-甲基咪唑、4-硝基咪唑、4-甲基哌啶、苄胺、N-(2-羟乙基)哌嗪、N-(2-氨乙基)哌嗪、2-甲基咪唑、苯并咪唑、5,6-二甲基苯并咪唑、N-乙基哌嗪。
其中，所述α，β－不饱和缺电子受体为丙烯腈、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯。
其中，所述反应介质为无反应介质
反应结束后，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，水相真空干燥后直接用于下一批次反应，离子液体可重复使用6次，未发现反应收率下降。
本发明提供的利用新型离子液体催化加成胺类和α，β－不饱和缺电子受体的方法，是通过以下途径来实现的：
本发明所使用的新型功能离子液体的制备过程(已另行申请专利)：
将DABCO(三乙烯二胺)和3-氯-1,2-丙二醇加入100mL圆底烧瓶中,加入50mL乙醇为溶剂。磁力搅拌下，80℃加热回流反应24h。旋蒸得到[DABCO-PDO][Cl]。向[DABCO-PDO][Cl]中加入等摩尔量的NaBF4(KPF6、CH3COOK、CF3SO3K)，加入15mL甲醇，65℃下，加热回流反应8h，后真空干燥得到淡黄色稠液体，即为离子液体[DABCO-PDO][BF4]([DABCO-PDO][PF6]、[DABCO-PDO][OAc]、[DABCO-PDO][CF3SO3])。制备的离子液体用1HNMR，13CNMR结构确认。四种离子液体分别为所述离子液体为：
简称为[DABCO-PDO][OAc]，
简称为[DABCO-PDO][BF4]，
简称为[DABCO-PDO][PF6]，
简称为[DABCO-PDO][CF3SO3]。
Michael加成产物制备过程是：
在装有磁力搅拌装置的单口烧瓶中，依次加入胺类、α，β－不饱和缺电子受体和离子液体。其中胺类与α，β－不饱和缺电子受体的摩尔比为1:1-1:2，离子液体与胺类的摩尔比为0.01:1-1:1，室温搅拌100-500分钟，薄层色谱(TLC)跟踪反应进度。反应结束后，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，水相真空干燥后直接用于下一批次反应，无需补加新鲜离子液体，离子液体重复使用6次，未见收率下降。
该法操作简单、收率高、催化反应体系可重复使用性好、反应条件温和，具有良好的工业化前景。
具体实施方式
以下将结合实施例对本发明做进一步说明，本发明的实施例仅用于说明本发明的技术方案，并非限定本发明。
实施例1
将咪唑(5mmol)、丙烯酸甲酯(6mmol)、2mmol离子液体[DABCO-PDO][OAc]依次加入到50mL单口瓶中，室温搅拌300分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率93％，含量98％。methyl3-(1H-imidazol-1-yl)propanoate:1HNMR(400MHz,CDCl3)(ppm):2.72(t,2H,J＝6Hz),3.62(s,3H),4.20(t,2H,J＝2.4Hz),6.86(d,1H,J＝4.4Hz),6.95(d,1H,J＝6Hz),7.43(d,1H,J＝4.8Hz)；13CNMR(100MHz,CDCl3)(ppm):170.84,137.10,129.17,118.75,51.77,42.00,35.46.
实施例2
将咪唑(5mmol)、甲基丙烯酸甲酯(6mmol)、2mmol离子液体[DABCO-PDO][CF3SO3]依次加入到50mL单口瓶中，室温搅拌300分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率88％，含量98％。methyl3-(1H-imidazol-1-yl)butanoate:1HNMR(400MHz,CDCl3)(ppm):1.19(d,3H,J＝6.8Hz),2.86-2.91(m,1H),3.67(s,3H),3.78(t,1H,J＝4.4Hz),4.00-4.05(m,1H),6.92(s,1H),7.04(s,1H),7.50(s,1H)；13CNMR(100MHz,CDCl3)(ppm):14.85,41.26,49.24,52.16,121.68,128.91,135.20,174.13.
实施例3
将4-甲基咪唑(5mmol)、丙烯酸甲酯(6mmol)、2mmol离子液体[DABCO-PDO][PF6]依次加入到50mL单口瓶中，室温搅拌300分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率90％，含量98％。methyl3-(4-methyl-1H-imidazol-1-yl)propanoate:1HNMR(400MHz,CDCl3)(ppm):1.78(d,3H,J＝12.9Hz),2.39–2.28(m,2H),3.25(s,3H),3.83–3.70(m,2H),6.29(d,1H,J＝12.4Hz),7.03(d,1H,J＝25.2Hz)；13CNMR(100MHz,CDCl3)(ppm):13.09,35.21,41.73,51.47,115.00,136.09,137.68,170.81.
实施例4
将4-硝基咪唑(5mmol)、丙烯酸甲酯(6mmol)、2mmol离子液体[DABCO-PDO][BF4]依次加入到50mL单口瓶中，室温搅拌270分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率91％，含量97％methyl3-(4-nitro-1H-imidazol-1-yl)propanoate；1HNMR(400MHz,CDCl3)(ppm):δ＝2.88(t,2H,J＝6Hz),3.73(s,3H),4.38(t,2H,J＝6Hz),7.53(s,1H),7.87(s,1H)；13CNMR(100MHz,CDCl3)(ppm):35.1,43.5,52.5,119.5,136.4,148.2,170.5.
实施例5
将咪唑(5mmol)、丙烯酸乙酯(6mmol)、2mmol离子液体[DABCO-PDO][BF4]依次加入到50mL单口瓶中，室温搅拌270分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率90％，含量97％。ethyl3-(1H-imidazol-1-yl)propanoate；1HNMR(400MHz,CDCl3)(ppm):1.08(t,3H,J＝7.2Hz),2.62-2.64(m,2H),3.99(t,2H,J＝6Hz),4.13(t,2H,J＝6Hz),6.80(d,1H,J＝6Hz),6.87(d,1H,J＝4.8Hz),7.36(d,1H,J＝6.8Hz)；13CNMR(100MHz,CDCl3)(ppm):14.04,35.94,42.26,61.09,118.86,129.43,137.22,170.51
实施例6
将咪唑(5mmol)、丙烯酸丁酯(6mmol)、2mmol离子液体[DABCO-PDO][BF4]依次加入到50mL单口瓶中，室温搅拌270分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率88％，含量98％。butyl3-(1H-imidazol-1-yl)propanoate；1HNMR(400MHz,CDCl3)(ppm):0.76(t,3H,J＝7.6Hz),1.18(d,2H,J＝7.6Hz),1.41(d,2H,J＝7.6Hz),2.62(t,2H,J＝6.8Hz),3.93(t,2H,J＝6.4Hz),4.11(t,2H,J＝6.8Hz),6.80(s,1H),6.87(s,1H),7.35(s,1H)；13CNMR(100MHz,CDCl3)(ppm):162.7,155.0,144.6,131.2,130.0,128.8,115.7,101.4,62.5,21.8,14.1.
实施例7
将咪唑(5mmol)、甲基丙烯酸丁酯(6mmol)、2mmol离子液体[DABCO-PDO][BF4]依次加入到50mL单口瓶中，室温搅拌270分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率83％，含量98％。butyl3-(1H-imidazol-1-yl)butanoate；1HNMR(400MHz,CDCl3)(ppm):0.87(t,3H,J＝7.6Hz),1.16(d,3H,J＝7.2Hz),1.26-1.35(m,2H),1.51-1.59(m,2H),2.81-2.90(m,1H),3.96-4.03(m,1H),4.04-4.07(m,2H),4.20-4.25(m,1H),6.89(s,1H),7.02(s,1H),7.45(s,1H)；13CNMR(100MHz,CDCl3)(ppm):13.55,14.84,18.92,30.38,41.40,49.16,64.84,119.22,129.18,137.44,173.72.
实施例8
将咪唑(5mmol)、丙烯腈(6mmol)、2mmol离子液体[DABCO-PDO][OAc]依次加入到50mL单口瓶中，室温搅拌160分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率94％，含量98％。3-(1H-imidazol-1-yl)propanenitrile:1HNMR(400MHz,CDCl3)(ppm):2.72-2.75(m,2H),4.13-4.16(m,2H),6.94(d,2H,J＝4.4Hz),7.49(s,1H)；13CNMR(100MHz,CDCl3)(ppm):20.5,42.5,116.8,118.7,130.1,137.0.
实施例9
将吡唑(5mmol)、丙烯腈(6mmol)、2mmol离子液体[DABCO-PDO][OAc]依次加入到50mL单口瓶中，室温搅拌160分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率94％，含量98％。3-(1H-pyrazol-1-yl)propanenitrile:1HNMR(400MHz,CDCl3)(ppm):2.91-2.95(m,2H),4.39(t,2H,J＝5.6Hz),6.29(t,1H,J＝1.2Hz),7.49(d,1H,J＝2Hz),7.56(s,1H)；13CNMR(100MHz,CDCl3)(ppm):10.3,47.3,106.2,117.3,129.9,140.6
实施例10
将2-甲基咪唑(5mmol)、丙烯酸甲酯(6mmol)、2mmol离子液体[DABCO-PDO][OAc]依次加入到50mL单口瓶中，室温搅拌300分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率90％，含量97％。methyl3-(2-methyl-1H-imidazol-1-yl)propanoate:1HNMR(400MHz,CDCl3)(ppm):2.32(d,3H,J＝12.8Hz),2.66-2.71(m,2H),3.62(d,3H,J＝13.2Hz),4.10-4.13(m,2H),6.77-6.85(m,2H),7.29(s,1H)；13CNMR(100MHz,CDCl3)(ppm):12.88,35.135,41.26,51.99,118.86,127.44,144.40,170.84
实施例11
将吗啉(5mmol)、丙烯酸甲酯(6mmol)、2mmol离子液体[DABCO-PDO][OAc]依次加入到50mL单口瓶中，室温搅拌100分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率95％，含量98％。methyl3-morpholinopropanoate:1HNMR(400MHz,CDCl3)(ppm):2.42(t,4H,J＝4.8Hz),2.48(t,2H,J＝6.4Hz),2.65(t,2H,J＝7.2Hz),3.66(t,7H,J＝2.8Hz)；13CNMR(100MHz,CDCl3)(ppm):31.62,51.47,53.15,53.69,66.65,172.62.
实施例12
将4-甲基哌啶(5mmol)、丙烯酸甲酯(6mmol)、2mmol离子液体[DABCO-PDO][OAc]依次加入到50mL单口瓶中，室温搅拌100分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率93％，含量98％。methyl3-(4-methylpiperidin-1-yl)propanoate；1HNMR(400MHz,CDCl3)(ppm):0.95(d,3H,J＝6.0Hz)1.35-1.41(m,2H),1.68-1.71(m,2H),2.03(s,1H),2.16-2.21(m,2H),2.65(t,2H,J＝7.2Hz),2.87(t,2H,J＝7.6Hz),3.04(d,2H,J＝10.6Hz),3.07(s,3H)；13CNMR(100MHz,CDCl3)(ppm):21.6,30.2,31.1,33.1,51.9,53.3,53.4,172.6.
实施例13
将N-(2-羟乙基)哌嗪(5mmol)、丙烯腈(6mmol)、2mmol离子液体[DABCO-PDO][OAc]依次加入到50mL单口瓶中，室温搅拌100分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率92％，含量98％。3-(4-(2-hydroxyethyl)piperazin-1-yl)propanenitrile：1HNMR(400MHz,CDCl3)(ppm):2.52(t,2H,J＝7.2Hz),2.57(t,8H,J＝5.2Hz),2.71(t,2H,J＝6.8Hz),2.95(d,2H,J＝12.8Hz),3.63(t,2H,J＝4.6Hz)；13CNMR(100MHz,CDCl3)(ppm):15.9,52.6,52.7,53.2,57.7,59.3,118.7.
实施例14
将N-(2-氨乙基)哌嗪(5mmol)、丙烯腈(6mmol)、2mmol离子液体[DABCO-PDO][OAc]依次加入到50mL单口瓶中，室温搅拌100分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率92％，含量98％。methyl3-(4-(2-aminoethyl)piperazin-1-yl)propanenitrile：1HNMR(400MHz,CDCl3)(ppm):2.50-2.53(m,8H),2.71(t,4H,J＝6.8Hz),2.93(d,1H,J＝6.8Hz),3.60-3.61(m,1H),3.72-3.74(m,1H)；13CNMR(100MHz,CDCl3)(ppm):11.88,15.80,52.20,52.42,52.51,53.31,118.76.
实施例15
将N-乙基哌嗪(5mmol)、丙烯腈(6mmol)、2mmol离子液体[DABCO-PDO][OAc]依次加入到50mL单口瓶中，室温搅拌100分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率91％，含量98％。3-(4-ethylpiperazin-1-yl)propanenitrile：1HNMR(400MHz,CDCl3)(ppm):1.08(t,3H,J＝7.2Hz),2.40-2.45(m,2H),2.50-2.56(m,8H),2.71(t,2H,J＝6.8Hz),3.19-3.39(m,2H)；13CNMR(100MHz,CDCl3)(ppm):11.88,15.80,52.20,52.42,52.51,53.31,118.76.
实施例16
将苯并咪唑(5mmol)、丙烯酸甲酯(6mmol)、2mmol离子液体[DABCO-PDO][OAc]依次加入到50mL单口瓶中，室温搅拌100分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率90％，含量98％。methyl3-(1H-benzo[d]imidazol-1-yl)propanoate：1HNMR(400MHz,CDCl3)(ppm):2.53(t,2H,J＝6.4Hz),3.32(s,3H),4.11(t,2H,J＝6.4Hz),7.00-7.03(m,1H),7.58-7.59(m,1H),7.72(s,1H)；13CNMR(100MHz,CDCl3)(ppm):33.78,40.00,51.69,109.38,119.99,121.95,122.75,133.22,143.34,143.53,170.89
实施例17
将5,6-二甲基苯并咪唑(5mmol)、丙烯酸甲酯(6mmol)、2mmol离子液体[DABCO-PDO][OAc]依次加入到50mL单口瓶中，室温搅拌100分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率90％，含量98％。methyl3-(5,6-dimethyl-1H-benzo[d]imidazol-1-yl)propanoate：1HNMR(400MHz,CDCl3)(ppm):1.98(d,6H,J＝7.6Hz),2.44(t,2H,J＝6.4Hz),3.24(s,3H),.3.95(t,2H,J＝6.8Hz),6.79(s,1H),7.22(s,1H),7.50(s,1H)；13CNMR(100MHz,CDCl3)(ppm):20.06,33.68,39.83,61.43,109.40,119.85,130.50,131.62,131.71,142.11,142.38,170.83.
实施例18
将苄胺(5mmol)、丙烯酸甲酯(6mmol)、2mmol离子液体[DABCO-PDO][OAc]依次加入到50mL单口瓶中，室温搅拌100分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，收率85％，含量98％。methyl3-(benzylamino)propanoate：1HNMR(400MHz,CDCl3)(ppm):1.81(s,1H),2.55(t,2H,J＝6.4Hz),2.91(t,2H,J＝6.4Hz),3.69(s,3H),7.25-7.28(m,1H),7.33(t,4H,J＝4.4Hz)；13CNMR(100MHz,CDCl3)(ppm):34.55,44.45,51.60,53.76,126.98,128.01,128.42,140.13,173.22.
实施例19
将咪唑(5mmol)、丙烯酸甲酯(6mmol)、2mmol离子液体[DABCO-PDO][OAc]依次加入到50mL单口瓶中，室温搅拌300分钟TLC检测，加入乙酸乙酯溶解，再加入水进行萃取，有机相柱层析得产品，水相高温真空烘干后，继续投入使用，循环使用6次，未发现明显活性损失，产品收率93％，含量98％。methyl3-(1H-imidazol-1-yl)propanoate:1HNMR(400MHz,CDCl3)(ppm):2.72(t,2H,J＝6Hz),3.62(s,3H),4.20(t,2H,J＝2.4Hz),6.86(d,1H,J＝4.4Hz),6.95(d,1H,J＝6Hz),7.43(d,1H,J＝4.8Hz)；13CNMR(100MHz,CDCl3)(ppm):170.84,137.10,129.17,118.75,51.77,42.00,35.46.
表1
需要说明的是，上述发明内容及具体实施方式意在证明本发明所提供技术方案的实际应用，不应解释为对本发明保护范围的限定。本领域技术人员在本发明的精神和原理内，当可作各种修改、等同替换、或改进。本发明的保护范围以所附权利要求书为准。

Claims (8)

1.离子液体催化胺类与α，β－不饱和缺电子受体进行反应的方法,其特征在于，所述方法包括以离子液体为催化剂，无溶剂、室温、常压下胺类和α，β－不饱和缺电子受体进行催化加成反应，得到相应的加成产物；其中，所述离子液体为：
2.如权利要求1所述的方法，其特征在于，所述胺类与α，β－不饱和缺电子受体的摩尔比为1:1～1:2。
3.如权利要求1所述的方法，其特征在于，所述离子液体的摩尔量为胺类的0.01～1倍。
4.如权利要求1、2或3所述的方法，其特征在于，所述胺类为吗啉、咪唑、吡唑、4-甲基咪唑、4-硝基咪唑、4-甲基哌啶、苄胺、N-(2-羟乙基)哌嗪、N-(2-氨乙基)哌嗪、2-甲基咪唑、苯并咪唑、5,6-二甲基苯并咪唑、N-乙基哌嗪。
5.如权利要求1或2所述的方法，其特征在于，所述α，β－不饱和缺电子受体为丙烯腈、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯。
6.如权利要求1所述的方法，其特征在于，反应时间为100～500分钟。
7.如权利要求1或6所述的方法，其特征在于，反应结束后加入乙酸乙酯，再加入水萃取，萃取相干燥后可作为催化反应体系重复多次使用。
8.如权利要求7所述的方法，其特征在于，所述萃取相为包含离子液体的水相。
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